Cyanacetylamino phenol color formers for color photography



Patented May 11, 1948 CYANAGETYLAMINO PHENOL COLOR FORM- ERS FOR COLOR PHOTOGRAPHY John David Kendall and Douglas James-Fry, Ilford, England, assignors to Ilford Limited, Ilford, England, a British-companyv No Drawing. Application May 3, 1945, Serial No.

591,828. In Great Britain May 12, V

8 Claims.

1 p This invention relates to colour photography and particularly to dyestuff intermediates for use in colour photographic processes.

Processes of colour. photography are well known in which coloured images are produced by the development of reducible silver salt images by means of aromaticprimary amino develop-' ing agents in the presence of compounds, generally known as colour-formers" or colourcouplers, which couple with theoxidation products of such developers, formed during development, to form quinone-imine or azomethine dyes. The colour-couplers may be present in the developing solution employed, or may be included in a photographic emulsion layer which contains the reducible silver salt image, or in an adjacent layer or a layer separated from the said emulsion layer only by a thin Water-permeable layer. Thedeveloping agent may be, for example, p-phenylene diamine or its N.N.-dialkyl derivatives, e. g. N.N.-dimethyl and N.N.-diethyl p-ph'enylene diamines, or a homologue, e. g. 5-diethylamino-2- amino-toluene.

Large numbers of colour-couplers have been described in the extensive literature dealing with this type of colour photographic process. The requirements for a satisfactory colour-coupler, however, are rather strict. Thus it must be capable of ready incorporation into the developing bath or photographic layer'into which itis desired to include it, and where it is included ina photographic layer, neither it nor the dye derived from it must have any substantial tendency to diffuse from such layer, either into adjacent layers of the photographic element, or into processing baths. Moreover, it must be selected so that thecolourTof the dye obtained from it issuitable for the particular colour process with which it is intended to be used. 4

According to the present invention ja'process of colour photography comprises developing a reducible silver. salt image by means of an aro-v matic primary amino developing agent in the presence of a cyanaetylamino phenol of the general formula:

phonic, carboxyl, or halogen (or other atom or group readily removed during the dye-coupling reaction), or in the presence of a correspondin naphthol or higher homologous compound.

7 Such compoundsmay be prepared by reacting together an aminophenol (or naphthol or higher homologous compound) 'which is unsubstituted in' the para position tothe hydroxy group, or contains i a carboxyLsulphonic, halogen or other easily removable atom'or group in such position, with ethyl cyanacetate. Thus, for example, cyanacet-o-hydroxy-anilide may be prepared from o-amino-phenol and 'ethylcyanacetate in hot xylene solution in the presence of piperidine or other base. The'product separates on cooling, and after purification has a melting point of 178" 0. Similarly, using 2-amino-5-methyl phenol, the compound cyan'acet-o-h'ydroxy-p-toluidine, M.Pt. 189 C., is obtained. Both these compounds yield deep blue to blue-green dyes on colour-coupling development in accordance with thisinvention. Y

Other amino phenols and ,amino naphthols which may be similarly employed as initial reagents .are; for example, m-amino-phenol, 3- amino-e-naphthol, ,2-amino-5-ethoxy phenol, 2- amino-3-methyl 'phenol and 2-amino-5-chlor ph'enol. 1

Particular compounds which may be employed arez' 1-cyanacetylamino-2ehydroxy-l-ethoxy benzene 2-cyan'acetylamino l-hydroxy naphthalene I-cyanacetyIaminO-2-hydroxy-6-methyl benzene These compounds are made by the general process described above, using the appropriate reagents.

As will be clear from the foregoing discussion of the compounds, the benzene, naphthalene or other ring system present may'contain other substituent groups, e; g. hydrocarbon groups or alkoxy groups. 1 The colour-couplers of this invention maybe included in a developing solution containin an aromatic primary amino developing agent, or may be included in a silver halide emulsion layer, or in a water-permeable colloid layer coated next to a silver halide emulsion layer, or separated therefrom only by a thin water-permeable layer. Thus, for example, the colour-couplers of this invention may be used in any of the colour processes of U. S. Patents Nos. 2,350,380, 2,363,764 and 2,369,171 and British Patents Nos. 551,116, 551,117, 554,302 and 556,858.

The formation of coloured images by means of the colour-couplers of this invention may be applied to the development of a reducible silver salt image which is an original latent image formed in the emulsion layer by exposure to light, or which is an image obtained by the conversion of a silver image to areducible silver salt i a e by the usual ble hin techni ue;

Although this invention is primarily concerned with colour photographic processes in which the dye is formed by the coupling of the colourcouplers of the invention with the endatienprednets of an aromatic primary amino developing agent formed in situ during the deyeiopment, of a reducible silver salt image, ;th'e colours-couplers of the invention may also be employed in other colour photographic processes, ,e, g, .processesin which the dye is formed by direct coupling between the colour-coupler and a nitroso aniline, e. g. penitroso dialkyl aniline, or between the colour-coupler and a diazo compound. As an examp e f. t s latter time Qf.- processes 9191. 1:- up er m be P s nt in a layer so aim-nee e bl si e t ima e, s ch mage .1: oped w th ar mat c p imary i lino dev. opin age trermin an a omethi idyeimase .situ with t e dev lop dsi er ima e, the esidua o o ler c p d it .;.a diet-to compound ppl di ution, t the ph tos arms el ment and t e n l az meth ne .de image bleached out, eavi only he az .dyeuiinage n the layer.

What-We claim 7 V 1. A process of c lour photegraphy which coinprises developing a, redlleibie silver salt image in a photograph c elementby means of. an arsomatie p imary amine eerelep ng a enti the presence of a c mpound oi v-thesenerel formul where the hydroxy group in a position taken from the group consisting of ortho and meta positions to the cyanacetylaminogroup andwhere ;X. is para to the hydroxy group and, is a member se, lected from the class consisting of the hydrogen and halogen atoms and 'sulphonic and carboxyl groups. I r .l 2, A process of colour photography which comprises developing a reducible silver salt in a pho tographic element by means ore solution of an aromatic primary amino developing agent containing a compoundei t g neral o mu V NH.CO.CH2.CN

from the group consisting of ortho and meta positions to the cyanacetylamino group and where X is para to the hydroxy group and is a member selected from the class consisting of the, hydrogen and halogen atoms and-sulphonic ande r ox l g ups. 1

4. A photographic element for colour photography which comprises a support bearing at least one layer of a light-sensitive silver halide emulsign and, adjacent thereto, a layer containing a compound of the general formula:

NH.OO.CH2.CN

where the hydroxy group is in a position taken frorn the group consisting of ortho and meta positions to the cyanacetylamino group and where X para to the hydroxy group and is a member selected from the class consisting .of the ydrogen 'andhalo en atoms and su phonic and carboxyl groups. v p i v V .5 A proeess'o colour ph t g aphy which comprises forming a reducible silver salt image in an emulsion layer of .a photographic element which contains a, compound oi the general formula:

where the hydroxy group is in a position taken from the group consisting of ortho and meta positions to the cyanacetylamino group and where X s para to the hydroxy group and is a member selected from the classiconsisting of the hydrogen and halogen atoms and sulphonic and carboxyl groups, and developing said image with an aromatic primary amino developing agent.

6. A process of colour photography which comprises forming a reducible silver salt image in an emulsion layer of a photographic element which contains a compound of the general formula:

where the hydroxy group is in a position taken from the group consisting of ortho and meta positions to the cyanacetylamino group and where X is para to the hydroxy group and is a member selected from the class consisting of the hydrogen and halogenatoms and sulphonic and carboxyl groups, and developing said image with an -N,N-dialky1-p-phenylene diamine. i i 7. A process of colour photography which com prises forming a reducible silver salt image in an emulsionilayer of a photographic element which includes, adjacent thereto, a layer containing a compound of the general formula:

' ATNHD 0.0Hz.CN

where the hydroxy group is in a position taken from the group consisting of ortho and meta positions to the cyanacetylamino group and where X is para to the hydroxy group and is a memberseleoted from the class consisting of the hydrogen and halogen atoms and sulphonic and carboxyl groups, and developing said image with an aromatic primary. amino developing agent,-

8. A process of colour photography which comprises torming a reducible silver salt image in an emulsion layer of a photographic element which includes, adjacent thereto, a layer containing a com ound of the general formula:

NH.CO.CH1.CN

where the hydroxy group is in a. position taken from the group consisting of ortho and meta positions to the cyanacetylamino group and where X is para to the hydroxy group and is a member selected from the class consisting of the hydrogen and halogen atoms and sulphonic and carboxyl groups, and developing said image with an N,N-dialkyl-p-phenylene diamine.

JOHN DAVID KENDALL. DOUGLAS'JAMES FRY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

